Photoacoustic spectroscopy for trace gas detection with cryogenic and room-temperature continuous-wave quantum cascade lasers

The main characteristics that a sensor must possess for trace gas detection and pollution monitoring are high sensitivity, high selectivity and the capability to perform in situ measurements. The photacoustic Helmholtz sensor developed in Reims, used in conjunction with powerful Quantum Cascade Lasers (QCLs), fulfils all these requirements. The best cell response is # 1200 V W⁻¹ cm and the corresponding ultimate sensitivity is j 3.3 × 10⁻¹⁰ W cm⁻¹¹ Hz^−11/2. This efficient sensor is used with mid-infrared QCLs from Alpes Lasers to reach the strong fundamental absorption bands of some atmospheric gases. A first cryogenic QCL emitting at 7.9 μm demonstrates the detection of methane in air with a detection limit of 3 ppb. A detection limit of 20 ppb of NO in air is demonstrated using another cryogenic QCL emitting in the 5.4 μm region. Real in-situ measurements can be achieved only with room-temperature QCLs. A room-temperature QCL emitting in the 7.9 μm region demonstrates the simultaneous detection of methane and nitrous oxide in air (17 and 7 ppb detection limit, respectively). All these reliable measurements allow the estimated detection limit for various atmospheric gases using quantum cascade lasers to be obtained. Each gas absorbing in the infrared may be detected at a detection limit in the ppb or low-ppb range.     

Photoacoustic spectroscopy of solids

The opto- or photo-acoustic effect used in gas analysis has been extended to the study of solids. This technique provides a simple method for obtaining information about optical absorptions and subsequent de-excitations in solids.     

Evaluation of ammonia absorption coefficients by photoacoustic spectroscopy for detection of ammonia levels in human breath

Photoacoustic spectroscopy represents a powerful technique for measuring extremely low absorptions independent of the path length and offers a degree of parameter control that cannot be attained by other methods. We report precise measurements of the ammonia absorption coefficients at the CO₂ laser wavelengths by using a photoacoustic (PA) cell in an extracavity configuration and we compare our results with other values reported in the literature. Ammonia presents a clear fingerprint spectrum and high absorption strengths in the CO₂ wavelengths region. Because more than 250 molecular gases of environmental concern for atmospheric, industrial, medical, military, and scientific spheres exhibit strong absorption bands in the region 9.2–10.8 μm, we have chosen a frequency tunable CO₂ laser. In the present work, ammonia absorption coefficients were measured at both branches of the CO₂ laser lines by using a calibrated mixture of 10 ppm NH₃ in N₂. We found the maximum absorption in the 9 μm region, at 9R(30) line of the CO₂ laser. One of the applications based on the ammonia absorption coefficients is used to measure the ammonia levels in exhaled human breath. This can be used to determine the exact time necessary at every session for an optimal degree of dialysis at patients with end-stage renal disease.     

Photoacoustic spectroscopy using quantum-cascade lasers

Photoacoustic spectra of ammonia and water vapor were recorded by use of a continuous-wave quantum-cascade distributed-feedback (QC-DFB) laser at 8.5 mum with a 16-mW power output. The gases were flowed through a cell that was resonant at 1.6 kHz, and the QC-DFB source was temperature tuned over 35 nm for generation of spectra or was temperature stabilized on an absorption feature peak to permit real-time concentration measurements. A detection limit of 100 parts in 10(9) by volume ammonia at standard temperature and pressure was obtained for a 1-Hz bandwidth in a measurement time of 10 min.     

Automatically tunable continuous-wave optical parametric oscillator for high-resolution spectroscopy and sensitive trace-gas detection

We present a high-power (2.75 W), broadly tunable (2.75–3.83 μm) continuous-wave optical parametric oscillator based on MgO-doped periodically poled lithium niobate. Automated tuning of the pump laser, etalon and crystal temperature results in a continuous wavelength coverage up to 450 cm^-1 per poling period at <5×10^-4 cm^-1 resolution. The versatility of the optical parametric oscillator as a coherent light source in trace-gas detection is demonstrated with photoacoustic and cavity ring-down spectroscopy. A 17-cm^-1-wide CO₂ spectrum at 2.8 μm and multi-component gas mixtures of methane, ethane and water in human breath were measured using photoacoustics. Methane (at 3.2 μm) and ethane (at 3.3 μm) were detected using cavity ring-down spectroscopy with detection limits of 0.16 and 0.07 parts per billion by volume, respectively. A recording of ¹²CH₄ and ¹³CH₄ isotopes of methane shows the ability to detect both species simultaneously at similar sensitivities. PACS 42.65.Yj; 42.72.Ai; 42.62.Fi     

Breath ammonia detection based on tunable fiber laser photoacoustic spectroscopy

A new detection method for ammonia in high concentration of CO₂ and H₂O is reported, which uses a wavelength modulated photoacoustic spectrometer based on a near-infrared tunable erbium-doped fiber laser in combination with an optical fiber amplifier. The multi-wavelength (1522.44 nm, 1522.94 nm and 1545.05 nm) photoacoustic signal measurement is established to detect multi-spectrum signal in samples. The problem of ammonia detection in high concentration of CO₂ and H₂O is resolved at atmospheric pressure. The minimum detection limit of 16 ppb (signal-to-noise ratio = 1) in simulated breath samples (5.3% CO₂ and 6.2% H₂O (100% relative humidity at 37°C)) is achieved.     

Photoacoustic spectroscopy analysis of silicon crystals

A high resolution fully automated photoacoustic spectrometer (PAS) of the gas-microphone type is used in the photon energy region 0.8–1.6 eV to analyze the optical properties of silicon single crystals at different frequencies between 25 and 312 Hz. At modulating frequencies at which the sample thickness approaches its thermal diffusion length, the results obtained of untreated specimens using different PA cells reveal the presence of several peaks in the absorption tail, some of which are independent of the photon energy. The magnitude of these peaks is seen to be stronger than that of the maximum of the fundamental edge of silicon, thus making it indistinct. At lower modulating frequencies at which the sample thickness is far less than its thermal diffusion length and using a highly reflecting backing material, multiple reflections of the light beam within the sample interfaces are seen to enhance the PA amplitude signal sensitivity response as predicted theoretically. The effect of etching silicon samples in a diluted solution of hydrofluoric acid (5%) on photoacoustic spectra has been investigated. It is observed that this process removes all spurious features in the spectra originating from the surface contaminants making the fundamental absorption edge clearly visible and leaving only one distinct peak at hν=0.9 eV. Transmission-photoacoustic (T-PAS) has also been used to study silicon single crystals. In the light of recent literature a comparison is carried out between the results obtained using the two techniques in determining the absorption coefficient and the gap energy.     

Photoacoustic infrared spectroscopy of some solids

Infrared spectra in the 100–15000 wavenumber region (0.67–100 m) of some ionic (as LiF) and semiconducting (as Ge, Si, GaAs) powders and crystals are reported. The experiment involves the use of a photoacoustic cell as an accessory to a multiple scan averaging Michelson interferometer. The results show the advantages of studying impurities in powders, and surface properties, particularly since the technique is immune to scattering induced errors.Work presented in part (by D.G.M.) at the 22nd Rocky Mountain Conference, Denver, CO, August 10–14, 1980.     

Open-path trace gas detection of ammonia based on cavity-enhanced absorption spectroscopy

A compact open-path optical ammonia detector is developed. A tunable external-cavity diode laser operating at 1.5 μm is used to probe absorptions of ammonia via the cavity-enhanced absorption (CEA) technique. The detector is tested in a climate chamber. The sensitivity and linearity of this system are studied for ammonia and water at atmospheric pressure. A cluster of closely spaced rovibrational overtone and combination band transitions, observed as one broad absorption feature, is used for the detection of ammonia. On these molecular transitions a detection limit of 100 ppb (1 s) is determined. The ammonia measurements are calibrated independently with a chemiluminescence monitor. Compared to other optical open-path detection methods in the 1–2 μm region, the present result shows an improved sensitivity for contactless ammonia detection by over one order of magnitude. Using the same set-up, a detection limit of 100 ppm (1 s) is determined for the detection of water at atmospheric pressure. Received: 19 January 2000 / Revised version: 6 March 2000 / Published online: 7 June 2000     

Photoacoustic spectroscopy of diamond powders and polycrystalline films

Photoacoustic spectroscopy is used to study optical absorption in diamond powders and polycrystalline films. The photoacoustic spectra of diamond powders with crystallite sizes in the range from ∼100 μm to 4 nm and diamond films grown by chemical vapor deposition (CVD) had a number of general characteristic features corresponding to the fundamental absorption edge for light with photon energies exceeding the width of the diamond band gap (∼5.4 eV) and to absorption in the visible and infrared by crystal-structure defects and the presence of non-diamond carbon. For samples of thin (∼10 μm) diamond films on silicon, the photoacoustic spectra revealed peculiarities associated with absorption in the silicon substrate of light transmitted by the diamond film. The shape of the spectral dependence of the amplitude of the photoacoustic signal in the ultraviolet indicates considerable scattering of light specularly reflected from the randomly distributed faces of the diamond crystallites both in the polycrystalline films and in the powders. The dependence of the shape of the photoacoustic spectra on the light modulation frequency allows one to estimate the thermal conductivity of the diamond films, which turns out to be significantly lower than the thermal conductivity of single-crystal diamond. Fiz. Tverd. Tela (St. Petersburg) 39, 1787–1791 (October 1997)     

Photoacoustic spectroscopy with quantum cascade distributed-feedback lasers

We present photoacoustic (PA) spectroscopy measurements of carbon dioxide, methanol, and ammonia. The light source for the excitation was a single-mode quantum cascade distributed-feedback laser, which was operated in pulsed mode at moderate duty cycle and slightly below room temperature. Temperature tuning resulted in a typical wavelength range of 3cm(-1)at a linewidth of 0.2cm(-1). The setup was based on a Herriott multipass arrangement around the PA cell; the cell was equipped with a radial 16-microphone array to increase sensitivity. Despite the relatively small average laser power, the ammonia detection limit was 300 parts in 10(9)by volume.     

Photoacoustic spectroscopy characterization of CdSe quantum rods

The application of the FT-IR/PAS technique for investigation of the chemical structure of poly(VPy-DVB), polyMAA and polyVPy were studied. The correlations between synthesis conditions (e.g. relatively comonomer molar ratios) and corresponding photoacoustic spectrum were studied. Additionally the influence of washing procedure on the properties of obtained polymer was examined.     

Photoacoustic spectroscopy analysis of thin semiconductor samples

This paper is an analysis of determination possibility of the optical absorption coefficient spectra of thin semiconductor layers from their normalized photoacoustic amplitude spectra. Influence of multiple reflections of light in thin layers on their photoacoustic and optical absorption coefficient spectra is presented and discussed in detail. Practical formulae for the optical absorption coefficient spectrum as a function of the normalized photoacoustic amplitude spectrum are derived and presented. Next, they were applied for computations of the optical absorption coefficient spectra of thin In₂S₃ thin layers deposited on a glass substrate. This method was experimentally verified with the optical transmission method.     

Photoacoustic detection of ferro and paramagnetic resonance

A commercial ESR spectrometer was modified to detect the photoacoustic signal of modulated magnetic resonance absorption, operating at room temperature and at atmospheric pressure. Both magnetically ordered materials (YIG and FeBO₃) and paramagnetic substances were investigated. The measurements include various phenomena of ferromagnetic resonance: uniform precession, magnetostatic modes and spin-wave instabilities. Paramagnetic resonance was observed in the concentrated system MnF₂ and in the diluted system ZnS : Mn (1%), with well resolved hyperfine splitting.     

Ultrafast photoelectron spectroscopy: Femtosecond pump-probe coincidence detection of ammonia cluster ions and electrons

A new type of experiment is described, in which the femtosecond pump-probe method is combined with the photoelectron-photoion coincidence technique and time-of-flight photoelectron energy analysis. The experimental conditions for observing true coincidences are discussed. The performance of the new time resolved, ultrafast photoelectron spectroscopy is exemplified by studying the excited state dynamics of ammonia molecules and clusters.     

Photoacoustic spectroscopy of solids immersed in transparent liquids

A method is developed to obtain the photoacoustic spectra of solids by immersing them in a liquid cell with a submersed tranducer and detecting the acoustic pulse generated due to bulk absorption of pulsed laser radiation in the solids. Proper choice of liquids enables spectra to be obtained which are independent of the optical properties of the solid surfaces of the surrounding liquid. This technique is compared to other established PAS methods.     

Photoacoustic X-ray absorption fine-structure spectroscopy of the NiK-edge

The X-ray absorption in a 5 m thick Ni foil for energies from 8.2 keV to 8.8 keV was measured by the photoacoustic method using a gas-microphone-cell. Results are presented for both photoacoustic amplitude and phase as a function of incident photon energy. The absorption fine structure above the NiK-edge is clearly resolved. The data are compared with a simple theory for the signal generation, and discrepancies are explained by discussing the various energy dissipation channels following the X-ray absorption.